The present invention relates to radically polymerizable compositions, containing at least one light stabilizer with an ethylenically unsaturated group and to oligomers, polymers, cooligomers or copolymers having low polydispersity Mw/Mn, which are prepared by controlled radical polymerization from the polymerizable composition. Further aspects of the invention are a process for their preparation, their use as light or heat stabilizers for organic materials, particularly for synthetic polymers, paints, enamels or varnishes and the organic materials thus stabilized.
The stabilization of polymers with light/heat stabilizers such as 2,2,6,6-tetramethylpiperidine derivatives, hydroxy-benzophenones, hydroxy-benzotriazoles and hydroxy-phenyl-s-triazines is well known. It is also known to prepare and to use oligomeric or polymeric light stabilizers of the above mentioned classes for the stabilization of polymers. This is for example described in U.S. Pat. No. 4,294,949 and in U.S. Pat. No. 4,785,063. These polymeric light stabilizers are all prepared by a conventional free radical polymerization process.
However polymers or copolymers prepared by free radical polymerization processes inherently have broad molecular weight distributions or polydispersities which are generally higher than about four. One reason for this is that most of the free radical initiators have half lives that are relatively long, ranging from several minutes to many hours, and thus the polymeric chains are not all initiated at the same time and the initiators provide growing chains of various lengths at any time during the polymerization process.
Due to the broad molecular weight distribution and high molecular weights of the polymeric light stabilizers problems arise when they are incorporated into paints, coatings, or thermoplastic polymers. They cause for example a strong viscosity increase in paints and coatings, which is undesirable for the paint""s application, in particular for the spray application of automotive coatings. In thermoplastic polymers compatibility problems may arise particularly with the high molecular weight portion of the polymeric light stabilizers. For these reasons polymeric light stabilizers having a low polydispersity are desirable for many applications.
The light stabilizers of the present invention are polymeric resin products having low polydispersity. The polymerization process proceeds with good monomer to polymer conversion efficiency, thus being also feasible on an industrial scale. In particular, this invention relates to stable free radical-mediated polymerization processes or to a, free radical initiated polymerization process by the ATRP (Atom Transfer Radical Polymerization) method which provide homopolymers, alternate-, gradient- or random copolymers, block copolymers or multiblock copolymers of different classes of light stabilizers.
The so made polymers or copolymers are highly compatible with thermoplastic polymers and thermosetting coatings. They are very efficient light/heat stabilizers either when used alone or in combination with other known stabilizers. Due to their low polydispersity they are easy to incorporate into other polymers, without for example significantly increasing their viscosity or melting properties.
One subject of the present invention is a polymerizable composition, comprising a) at least one compound of formula (I)
(RG)xe2x80x94Axe2x80x94(Stab)xe2x80x83xe2x80x83(I),
wherein
(Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxy-benzophenones; A is a spacer group or a direct bond; and
(RG) is a group containing at least one ethylenically unsaturated functional group; and either b1) a compound of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
xe2x80x83wherein
X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and
Y represents a group being such that the free radical Yxc2x7 derived from it forms a stable free radical; or b2) a stable free radical Yxc2x7 and a free radical source from which a radical is formed capable of initiating polymerization; or b3) a compound of formula (III) 
xe2x80x83and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
p represents a number greater than zero and defines the number of initiator fragments;
q represents a number greater than zero;
[In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I).
The sterically hindered amines are preferably selected from the class of piperidines, piperazinones, piperazindiones or morpholinones.
Preferably component a) of formula (I) is a compound of formulae (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii) or (Ij) 
W is O, or NR110;
A is a direct bond, xe2x80x94(C2-C12)alkylene-Wxe2x80x94, xe2x80x94(C3-C12)alkenylene-Wxe2x80x94, xe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94Wxe2x80x94, xe2x80x94(C3-C12)alkinylene-Wxe2x80x94, (C5-C12)cycloalkylene-Wxe2x80x94, xe2x80x94(C2-C12)alkylene-Wxe2x80x94 interrupted by at least one oxygen or nitrogen atom or a group xe2x80x94CH2xe2x80x94CHR110xe2x80x94Wxe2x80x94, a group xe2x80x94CHR111xe2x80x94COOP wherein P is xe2x80x94(CH2xe2x80x94HCR112)nxe2x80x94 or a group xe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94, wherein R110, R111, R112 and n are as defined below;
R110 is H or methyl R102 is hydrogen, OH, C1-C18alkyl, C3-C8alkenyl, C3-C8alkynyl; C7-C12aralkyl, C1-C18alkanoyl, C3-C18alkenoyl, C1-C18alkanoyloxy, glycidyl, C1-C18alkoxy, C5-C12cycloalkyl, C5-C12cycloalkoxy or a group xe2x80x94CH2CHR110(OH);
R103 is H, OH, NH2, C1-C18alkoxy, C1-C18alkanoyloxy, C6-C18aryloyloxy, C1-C18alkanoylamino, C1-C18alkylamino, C1-C18alkylamino, benzyloxy or together with the linking carbon atom forms a C5-C6cycloalkyl radical or a C5-C6heterocycloalkyl radical containing one or two oxygen or nitrogen atoms;
R104, R105, R106, R107 are independently C1-C8alkyl or C5-C12cyloalkyl, or R104 and R105 and/or R106 and R107 together with the carbon atom to which they are attached form-a C5-C12cycloalkyl group;
R108 and R109 independently are H, C1-C8alkyl or phenyl;
R110 is hydrogen, C1-C18alkyl or phenyl;
R111 is hydrogen or C1-C12alkyl;
R112 is hydrogen or methyl;
R201 and R202 are independently H, OH, CN, C1-C18alkyl, C1-C18alkoxy, halogen, C1-C18alkanoyl, C1-C18alkanoyloxy, C1-C18alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy or a group xe2x80x94Oxe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94OR206;
R203 and R204 are independently H, OH, CN, C1-C18alkyl, C1-C18alkoxy, halogen, C1-C18alkanoyl, C1-C18alkanoyloxy, C1-C18alkanoylamino, or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy or a group xe2x80x94Oxe2x80x94CH2xe2x80x94HC(OH)xe2x80x94CH2xe2x80x94OR206 with the proviso that at least one of both is OH;
R205 is H, halogen, phenyl, C1-C18alkyl, C5-C12cycloalkyl, C7-C12aralkyl or a group xe2x80x94SR208, xe2x80x94SO2R208, xe2x80x94COOR208 or PO(OR208)2;
R206 is C1-C18alkyl, C3-C18alkyl interrupted by at least one oxygen atom, phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl, C1-C18alkoxy, C5-C6cycloalkyl which is unsubstituted or substituted by C1-C4alkyl or a group xe2x80x94C(O)R207;
R207 C1-C18alkyl or phenyl which is unsubstituted or substituted with halogen, OH, CN, NO2, C1-C18alkyl or C1-C18alkoxy;
R208 is C1-C18alkyl, C5-C6cycloalkyl or phenyl;
R209 is H, halogen, phenyl, C1-C18alkyl, C5-C12cycloalkyl, C7-C12aralkyl or a group xe2x80x94SR208, xe2x80x94SO2R208, xe2x80x94COOR208 or PO(OR208)2;
n is a number from 0 to 12, and
k is a number from 0 to 12.
Preferably R108 and R109 are hydrogen and the other substituents are as defined above.
Preferably R104, R105, R106 and R107 are methyl and the other substituents are as defined above.
Preferably A is a direct bond, xe2x80x94(C2-C6)alkylene-Wxe2x80x94, xe2x80x94(C2-C12)alkylene-Wxe2x80x94 interrupted by at least one oxygen or nitrogen atom or a group xe2x80x94CH2xe2x80x94CHCH3xe2x80x94Wxe2x80x94.
W is preferably an oxygen atom.
R102 is preferably hydrogen, C1-C8alkyl, allyl, benzyl, C1-C8alkanoy), C1-C8alkanoyloxy, C1-C8alkoxy or cyclohexyloxy.
Preferably R103 is H, C1-C8alkoxy, C1-C8alkanoyloxy, benzyloxy, C1-C8alkylamino, C1-C8dialkylamino or C1-C8alkanoylamino.
R201, R202, R203 and R204 are independently H, C1-C8alkyl, OH, C1-C8alkoxy, phenyl or halogen, with the proviso that at least one of R203 or R204 is OH.
Preferably R205 is hydrogen, halogen or C1-C8alkyl.
Preferably R206 is C1-C4alkyl or phenyl.
R207 is preferably C1-C4alkyl or phenyl which is unsubstituted or substituted with C1-C18alkoxy;
R208 is pereferably C1-C4alkyl or phenyl;
Preferably n is a number from 2-6 and k is a number from 0-2.
Preferably the compound of formula (I) is a compound of formulae (Ia), (Ic), (Id), (If), (Ig), (Ii) or I(j), more preferably of formulae (Ia), (If), (Ig) or (Ii).
Preferred is a composition, wherein in the compound of formula (Ia), A is a direct bond, C2-C6alkylene or C2-C6alkylene interrupted by at least one oxygen or nitrogen atom; RG is a group 
W is an oxygen atom;
R101 is H or methyl
R102 is H, C1-C4alkyl, allyl, benzyl, C1-C6alkoxy, cyclohexyloxy, acetyl or acryloyl;
R104-R107 are methyl and
R108 and R109 are hydrogen.
Particularly preferred is a composition, wherein in the compound of formula (Ia), A is a direct bond; W is an oxygen atom; RG is a group 
R101 is H or methyl; R102 is H or C1-C4alkyl; R104-R107 are methyl; and R108 and R109 are hydrogen.
Also preferred is a composition, wherein in the compounds of formulae (If), (Ig) or (Ii)
A is a direct bond, C2-C6alkylene or C2-C6alkylene interrupted by at least one oxygen or nitrogen atom
W is an oxygen atom;
RG is a group 
R101 is H or methyl;
R201 and R202 are independently H, C1-C8alkyl, phenyl or OH;
R203 and R204 are independently H, C1-C8alkyl, phenyl or OH with the proviso that at least one of both is OH;
R205 is H, C1-C8alkyl or xcex1-cumyl;
R209 is H or Cl;
and k is a number from 1 to 8.
Particularly preferred is a composition, wherein in the compound of formula (Ii)
A is a direct bond
W is an oxygen atom;
RG is a group 
R101 is H or methyl;
R205 is H C1-C8alkyl, phenyl or xcex1-cumyl;
R209 is H or Cl and
k is a number from 1 to 8.
The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl oder n-4-octadecenyl.
Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 8 carbon atoms. C3-C8alkenyl can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.
Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl (xe2x80x94CH2xe2x80x94Cxe2x89xa1CH), 2-butinyl, 3-butinyl, n-2-octinyl, oder n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 8 carbon atoms. C3-C8alkynyl is most preferably propargyl.
Examples of C5-C12cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Preferred are cycloheptyl and cyclohexyl.
Examples of alkylene containing 1 to 18 carbon atoms are methylene, ethylene, propylene, isopropylene, butylene, 2-butylene, isobutylene, t-butylene, pentylene, 2-pentylene, hexylene, heptylene, octylene, 2-ethylhexylene, t-octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, hexadecylene and octadecylene.
C2-C18alkylene interrupted by at least one O atom is for example xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94 or xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94. It is preferably derived from polyethlene glycol. A general description is xe2x80x94((CH2)axe2x80x94O)bxe2x80x94/CH2xe2x80x94, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
Alkenylene with 3 to 18 carbon atoms is a linear or branched radical as for example propenylene, 2-butenylene, 3-butenylene, isobutenylene, n-2,4-pentadienylene, 3-methyl-2-butenylene, n-2-octenylene, n-2-dodecenylene, iso-dodecenylene, n-2-octadecenylene or n-4-octadecenylene.
Alkinylene with 3 to 18 is a linear or branched radical as for example propinylene, 2-butinylene, 3-butinylene, n-2-octinylene, or n-2-octadecinylene. C7-C9phenylalkyl is benzyl, phenylethyl or phenylpropyl, especially benzyl.
C1-C8alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and C3-C5alkenoyl is in particular acryloyl.
C1-C18alkanoyloxy is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.
C5-C7cycloalkylene is typically, cyclopentylene, methylcyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene or cyclopentylene.
Halogen is Fluorine, Chlorine, Bromine or Iodine, preferably Chlorine or Bromine.
In the compounds according to formula (Ib) R103 may form together with the linking carbon atom a C5-C6cycloalkyl radical or a C5-C6heterocycloalkyl radical containing one or two oxygen or nitrogen atoms. Typical examples are derived from
50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane
52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane
53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane
54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
55) 2,2,6,6-tetramethylpiperidine-4-spiro-2xe2x80x2-(1xe2x80x2,3xe2x80x2-dioxane)-5xe2x80x2-spiro-5xe2x80x3-(1xe2x80x3,3xe2x80x3-dioxane-2xe2x80x3-spiro-4xe2x80x2xe2x80x3-(2xe2x80x2xe2x80x3,2xe2x80x2xe2x80x3,6xe2x80x2xe2x80x3,6xe2x80x2xe2x80x3-tetramethylpiperidine) or from
56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione
59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione
60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione
61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane
64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane and preferably:
65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione
The composition may contain additional ethylenically unsaturated monomers or oligomers as component c).
Preferably the ethylenically unsaturated monomer or oligomer is selected from the group consisting of styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, (alkyl)acrylic acid anhydrides, acrylonitrile, (alkyl)acrylic acid salts, (alkyl)acrylic esters or (alkyl)acrylamides.
More preferably the ethylenically unsaturated monomer is i-butylene, styrene, xcex1-methyl styrene, p-methyl styrene or a compound of formula CH2xe2x95x90C(Ra)xe2x80x94(Cxe2x95x90Z)xe2x80x94Rb, wherein Ra is hydrogen or C1-C4alkyl, Rb is NH2, Oxe2x88x92(Me+), glycidyl, unsubstituted C1-C18alkoxy, C1-C18alkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C1-C18alkoxy, C1-C18alkoxy interrupted by at least one N and/or O atom, unsubstituted C1-C18alkylamino, di(C1-C18alkyl)amino; hydroxy-substituted C1-C18alkylamino or hydroxy-substituted di(C1-C18alkyl)amino, xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94N(CH3)2 or xe2x80x94Oxe2x80x94CH2xe2x80x94CH2xe2x80x94N+H(CH3)2 Anxe2x88x92;
Anxe2x88x92 is a anion of a monovalent organic or inorganic acid;
Me is amonovalent metal atom, NH4+ or HN+(C1-C4alkyl)3; and
Z is oxygen or sulfur.
More preferably the ethylenically unsaturated monomer is styrene, xcex1-methyl styrene, p-methyl styrene or a compound of formula CH2xe2x95x90C(Ra)xe2x80x94(Cxe2x95x90Z)Rb, wherein Ra, is hydrogen or C1-C4alkyl, Rb is NH2, Oxe2x88x92(Me+), glycidyl, unsubstituted C1-C18alkoxy or hydroxy-substituted C1-C18alkyloxy, unsubstituted C1-C18alkylamino, di(C1-C18alkyl)amino, hydroxy-substituted C1-C18alkylamino or hydroxy-substituted di(C1-C18alkyl)amino;
Me is a monovalent metal atom
Z is oxygen or sulfur.
Examples of monovalent metal atoms are Li, Na, K.
Examples of the anion Anxe2x88x92 of a monovalent organic or inorganic acid are C1-C18carbonic acid anions, the anions of HClO4, HCl or HBr.
Particularly preferred are monomers wherein Ra is hydrogen or methyl, Rb is NH2, gycidyl, unsubstituted or with hydroxy substituted C1-C4alkoxy, unsubstituted C1-C4alkylamino, di(C1-C4alkyl)amino, hydroxy-substituted C1-C4alkylamino or hydroxy-substituted di(C1-C4alkyl)amino; and
Z is oxygen.
Most preferably the ethylenically unsaturated monomer is methylacrylate, ethylacrylate, butylacrylate, isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate, hydroxypropylbutylacrylate, dimethylaminoethylacrylate, glycidylacrylates, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, glycidyl(meth)acrylates, acrylonitrile, acrylamide or methacrylamide.
Suitable compounds of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
free radicals Xxc2x7 and stable free radicals Yxc2x7 are known. Stable free radicals having a structural element 
are for example disclosed in EP-A-621 878.
Further examples such as 
are given in WO 96/24620.
Another suitable stable free radical, 1,3,5,5-Tetraphenyl-1,2,4-triazolin-2-yl, has been described by D. Colombani, M. Steenbock, M. Klapper, K. Mxc3xcllen in Macromol. Rapid. Commun. 18, 243-251 (1997). Further suitable compounds and their preparation are given in WO 99/03894, GB 2 335 190 and in PCT/EP 99/05377.
Initiator/regulator compounds of formula (II) containing a structural element 
are in principal known. Suitable compounds and their manufacture are for example described in U.S. Pat. No. 4,581,429, U.S. Pat. No. 5,721,320, U.S. Pat. No. 5,627,248, WO 98/13392, WO 98/30601 or in WO 98/44008.
The composition comprises preferably as component b1) a compound of formula (II)
Yxe2x80x94Xxe2x80x83xe2x80x83(II),
which contains a structural element 
wherein the nitrogen atom is part of a cyclic ring system or is substituted to form a acyclic structure.
A preferred acyclic structure is, wherein the compound containing a structural element 
is of formula (XXa), (XXb) or (XXc) 
wherein
Y1 is O or CH2;
Q1 is O or NR40, wherein R40 is hydrogen or C1-C18alkyl;
R21 is tertiary C4-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42 wherein R41 is hydrogen, a alkali metal atom or C1-C18alkyl and R42 is C1-C18alkyl; or
R21 is C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, a polycyclic alkyl radical or a polycyclic alkyl radical which is interrupted by at least one O or N atom;
R22 and R23 are independently C1-C18alkyl, benzyl, C5-C12cycloalkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42 or together with the carbon atom form a C5-C12cycloalkyl ring;
if Y1 is O, R24 and R32 are OH, O(alkali-metal) C1-C18alkoxy, benzyloxy, NR43R44, wherein R43 and R44 are independently from each other hydrogen, C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
if Y1 is CH2, R24 is OH, C1-C18alkoxy, benzyloxy, Oxe2x80x94C(O)xe2x80x94(C1-C18)alkyl or NR43R44;
R32 are a group C(O)R45, wherein R45 is OH, C1-C18alkoxy, benzyloxy, NR43R44, wherein R43 and R44 are independently from each other hydrogen, C1-C18alkyl or phenyl, which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
R25, R26, R27 and R28 are independently of each other C1-C18alkyl, C5-C12cycloalykyl or phenyl; or
R25 and R26 and/or R27 and R28 together with the carbon atom form a C5-C12cycloalkyl ring;
R29 and R30 are independently of each other hydrogen, C1-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42;
R31, is C1-C18alkylcarbonyl, benzoyl, C1-C18alkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is interrupted by at least one O or N atom, benzyl or phenyl which are unsubstituted or substituted by halogen, OH, COOR41 or C(O)xe2x80x94R42; and
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers.
Examples for the different substituents have been already given.
Typical examples of suitable compounds are given in Table 1. These compounds and there preparation is described in PCT/EP 99/05377.
Other suitable compounds with symmetrical substitution pattern are derived from nitroso compounds or nitrons and are described in WO 99/03894. Typical examples are given in Table 2. The nitroso and nitrone compounds can also be used as in situ precursors to form the compounds of Table 2 simultaneously to the polymerization step. This is described in WO 99/03894.
Preferably the initiator/regulator compounds form a cyclic structure 
which may be a 5, 6, 7 or 8 ring system having no hydrogen atom in xcex1-position to the nitrogen atom and which may contain one additional heteroatom in the ring.
Particularly suitable initiator/regulator compounds are 1-alkoxy-polyalkyl-piperidine derivatives containing a structural element of formula (X) 
G1, G2, G3, G4 are independently C1-C6alkyl with the proviso that at least one is not methyl or G1 and G2 or G3 and G4, or G1 and G2 and G3 and G4 together form a C5-C12cycloalkyl group;
G5, G6 independently are H, C1-C18alkyl, phenyl, naphthyl or a group COOC1-C18alkyl and
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers.
These compounds and their preparation are described in GB 2 335 190.
Particularly suitable compounds are listed in Table 3.
Another preferred class of initiators are those of formula (Xa) or (Xb) 
R1, R2, R3 and R4 independently of each other are C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by OH, halogen or a group xe2x80x94Oxe2x80x94 C(O)xe2x80x94R5, C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl or R1 and R2 and/or R3 and R4 together with the linking carbon atom form a C3-C12cycloalkyl radical;
R5, R6 and R7 independently are hydrogen, C1-C18alkyl or C6-C10aryl;
X represents a group having at least one carbon atom and is such that the free radical Xxc2x7 derived from X is capable of initiating polymerization of ethylenically unsaturated monomers;
Z1 is O or NR8;
R8 is hydrogen, OH, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl, C1-C18alkyl, C3-C18alkenyl, C3-C18alkinyl which are substituted by one or more OH, halogen or a group xe2x80x94Oxe2x80x94C(O)xe2x80x94R5, C2-C18alkyl which is interrupted by at least one O atom and/or NR5 group, C3-C12cycloalkyl or C6-C10aryl, C7-C9phenylalkyl, C5-C10heteroaryl, xe2x80x94C(O)xe2x80x94C1-C18alkyl, xe2x80x94Oxe2x80x94C1-C18alkyl or xe2x80x94COOC1-C18alkyl;
Q is a direct bond or a divalent radical CR9R10, CR9R10xe2x80x94CR11R12, CR9R10CR11R12CR13R14, C(O) or CR9R10C(O), wherein R9, R10, R11, R12, R13 and R14 are independently hydrogen, phenyl or C1-C18alkyl.
The compounds and their preparation are described in WO 98/30601, WO 98/44008 and in the British patent application No. 9923579.8.
Particularly useful are the compounds listed in Table 4, 5 and 6.
Preferably X is selected from the group consisting of 
(CH3)2xe2x80x94aryl, C5-C6cycloalkyl)2CCN, (C1-C12alkyl)2CCN, xe2x80x94CH2CHxe2x95x90CH2, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C12alkyl, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C6-C10aryl, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C12)alkoxy, (C1-C12)alkyl-CR20xe2x80x94C(O)-phenoxy, (C1-C12)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C12)alkyl, (C1-C12)alkyl-CR20xe2x80x94COxe2x80x94NH(C1-C12)alkyl, (C1-C12)alkyl-CR20xe2x80x94COxe2x80x94NH2, xe2x80x94CH2CHxe2x95x90CHxe2x80x94CH3, xe2x80x94CH2xe2x80x94C(CH3)xe2x95x90CH2, xe2x80x94CH2xe2x80x94
wherein
R20 is hydrogen or C1-C12alkyl;
the aryl groups are unsubstituted or substituted with C1-C12alkyl, halogen, C1-C12alkoxy, C1-C12alkylcarbonyl, glycidyloxy, OH, xe2x80x94COOH or xe2x80x94COOC1-C12alkyl.
More preferred are compounds, wherein X is selected from the group consisting of xe2x80x94CH2-phenyl, xe2x80x94CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, xe2x80x94CH2CHxe2x95x90CH2, CH3CHxe2x80x94CHxe2x95x90CH2, (C1-C8alkyl)CR20xe2x80x94C(O)-phenyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C8)alkoxy, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94NH(C1-C8)alkyl, (C1-C8)alkyl-CR20xe2x80x94C(O)xe2x80x94NH2, wherein R20 is hydrogen or (C1-C8)alkyl.
Particularly preferred are compounds, wherein X is selected from the group consisting of xe2x80x94CH2-phenyl, xe2x80x94CH3CH-phenyl, (CH3)2C-phenyl, (C5-C6cycloalkyl)2CCN, (CH3)2CCN, xe2x80x94CH2CHxe2x95x90CH2, CH3CHxe2x80x94CHxe2x95x90CH2, (C1-C4alkyl)CR20xe2x80x94C(O)-phenyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C4)alkoxy, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94N-di(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94NH(C1-C4)alkyl, (C1-C4)alkyl-CR20xe2x80x94C(O)xe2x80x94NH2, wherein R20 is hydrogen or (C1-C4)alkyl.
Another embodiment of the present invention is a composition, wherein component b3) is present as an alternative for b1) or b2).
A suitable component b3) contains a compound of formula (III), 
with a radically transferable atom or group xc2x7Hal as is described in WO 96/30421 and WO 98/01480. A preferred radically transferable atom or group xc2x7Hal is xc2x7Cl or xc2x7Br, which is cleaved as a radical from the initiator molecule.
Preferably [In] represents the polymerization initiator fragment of a polymerization initiator of formula (III), 
capable of initiating polymerization of monomers or oligomers which polymerization initiator is selected from the group consisting of C1-C8-alkyl halides, C6-C15-aralkylhalides, C2-C8xcex1-haloalkyl esters, arene sulfonyl chlorides, haloalkanenitrites, xcex1-haloacrylates and halolactones, p and q represent one and the other components are as defined above.
The polymerization process in the presence of a compound of formula (III) is known as ATRP (Atom Transfer Radical Polymerization) and WO 96/30421 discloses a controlled or xe2x80x9clivingxe2x80x9d polymerization process of ethylenically unsaturated polymers such as styrene or (meth)acrylates by employing the ATRP method. According to this method initiators are employed which generate a radical atom such as xc2x7Cl, in the presence of a redox system of transition metals of different oxidation states, e.g. Cu(I) and Cu(II), providing xe2x80x9clivingxe2x80x9d or controlled radical polymerization.
Specific initiators are selected from the group consisting of xcex1,xcex1xe2x80x2-dichloro- or xcex1,xcex1xe2x80x2-dibromoxylene, p-toluenesulfonylchloride (PTS), hexakis-(xcex1-chloro- or xcex1-bromomethyl)-benzene, 2-chloro- or 2-bromopropionic acid, 2-chloro- or 2-bromoisobutyric acid, 1-phenethyl chloride or bromide, methyl or ethyl 2-chloro- or 2-bromopropionate, ethyl-2-bromo- or ethyl-2-chloroisobutyrate, chloro- or bromoacetonitrile, 2-chloro- or 2-bromopropionitrile, xcex1-bromo-benzacetonitrile and xcex1-bromo-xcex3-butyrolactone (=2-bromo-dihydro-2(3H)-furanone).
The transition metal in the oxidizable transition metal complex catalyst salt used in the process of the invention is present as an oxidizable complex ion in the lower oxidation state of a redox system. Preferred examples of such redox systems are selected from the group consisting of Group V(B), VI(B), VII(B), VIII, IB and IIB elements, such as Cu+/Cu2+, Cu0/Cu+, Fe0/Fe2+, Fe2+/Fe3+, Ru2+/Ru3+, Ru3+/Ru4+, Os2+/Os3+, Vn+/V(n+1)+, Cr2+/Cr3+, Co+/Co2+, Co2+/Co3+, Ni0/Ni+, Ni+/Ni2+, Ni2+/Ni3+, Mn0/Mn2+, Mn2+/Mn3+, Mn3+/Mn4+, or Zn+/Zn2+.
The ionic charges are counterbalanced by anionic ligands commonly known in complex chemistry of transition metals, such hydride ions (Hxe2x88x92) or anions derived from inorganic or organic acids, examples being halides, e.g. Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, fluoro complexes of the type BF4xe2x88x92, PF6xe2x88x92, SbF6xe2x88x92 or AsF6xe2x88x92, anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadiene.
Anions of oxygen acids are, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C1-C4alkyl-, C1-C4alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methylphenylphosphonate or benzylphosphonate, carboxylates derived from a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, and also C1-C12-alcoholates, such as straight chain or branched C1-C12-alcoholates, e.g. methanolate or ethanolate. Anionic ligands and neutral may also be present up to the preferred coordination number of the complex cation, especially four, five or six. Additional negative charges are counterbalanced by cations, especially monovalent cations such as Na+, K+, NH4+ or (C1-C4 alkyl)4N+.
Suitable neutral ligands are inorganic or organic neutral ligands commonly known in complex chemistry of transition metals. They coordinate to the metal ion through a "sgr"-, xcfx80-, xcexc-, xcex7-type: bonding or any combinations thereof up to the preferred coordination number of the complex cation. Suitable inorganic ligands are selected from the group consisting of aquo (H2O), amino, nitrogen, carbon-monoxide and nitrosyl. Suitable organic ligands are selected from the group consisting of phosphines, e.g. (C6H5)3P, (i-C3H7)3P, (C5H9)3P or (C6H11)3P, di-, tri-, tetra- and hydroxyamines, such as ethylenediamine, ethylenediaminotetraacetate (EDTA), N,N-Dimethyl-Nxe2x80x2,Nxe2x80x2-bis(2-dimethylaminoethyl)-ethylenediamine (Me6TREN), catechol, N,Nxe2x80x2-dimethyl-1,2-benzenediamine, 2-(methylamino)phenol, 3-(methylamino)-2-butanol or N,Nxe2x80x2-bis(1,1-dimethylethyl)-1,2-ethanediamine, N,N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x3-pentamethyldiethyltriamine (PMDETA), C1-C8-glycols or glycerides, e.g. ethylene or propylene glycol or derivatives thereof, e.g. di-, tri- or tetraglyme, and monodentate or bidentate heterocyclic exe2x88x92 donor ligands.
Heterocyclic exe2x88x92 donor ligands are derived, for example, from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine, g-pyran, g-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene purine, bis-imidazole and bis-oxazole.
The oxidizable transition metal complex catalyst can be formed in a separate preliminary reaction step from its ligands or is preferably formed in-situ from its transition metal salt, e.g. Cu(I)Cl, which is then converted to the complex compound by addition of compounds corresponding to the ligands present in the complex catalyst, e.g. by addition of ethylenediamine, EDTA, Me6TREN or PMDETA.
Preferred is a composition, wherein in the component b3) the oxidizable transition metal in the transition metal complex salt is present as a transition metal complex ion in the lower oxidation state of a redox system.
More preferred is a composition, wherein the transition metal complex ion is a Cu(I) complex ion in the Cu(I)/Cu(II) system.
Another subject of the invention is a process for preparing an oligomer, cooligomer, polymer or copolymer with a polydispersity Mw/Mn between 1 and 3, which process comprises reacting a composition of a) at least one compound of formula (I)
(RG)xe2x80x94Axe2x80x94(Stab)xe2x80x83xe2x80x83(I),
wherein
(Stab) is a light stabilizer radical selected from the group consisting of sterically hindered amines, hydroxyphenyl-s-triazines, hydroxyphenyl-benzotriazols and o-hydroxybenzophenones; A is a spacer group or a direct bond; and
(RG) is a group containing at least one ethylenically unsaturated functional group; with either b1) a compound of formula (II)
Xxe2x80x94Yxe2x80x83xe2x80x83(II),
xe2x80x83wherein
X represents a group having at least one carbon atom and is such that the free radical derived from X is capable of initiating polymerization and
Y represents a group being such that the free radical derived from it forms a stable free radical or b2) a free radical source from which a radical Xxc2x7 is formed capable of initiating polymerization and a stable free radical Yxc2x7; or b3) a compound of formula (III)

xe2x80x83and a catalytically effective amount of an oxidizable transition metal complex catalyst, wherein
p represents a number greater than zero and defines the number of initiator fragments;
q represents a numeral greater than zero;
[In] represents a radically transferable atom or group capable of initiating polymerization and -[Hal] represents a leaving group; and optionally simultaneously or in a subsequent step with c) one or more ethylenically unsaturated monomers or oligomers different from those of formula (I), at a temperature between 50xc2x0 C. and 180xc2x0 C.
Preferably the temperature ranges from about 80xc2x0 C. to about 150xc2x0 C. At temperatures above about 180xc2x0 C., the controlled conversion of the monomers into polymers may decrease, and undesirable by-products like thermally initiated polymers are formed or decomposition of the components may occur.
The isolating step of the present process may be carried out by known procedures, e.g. by precipitation, distilling and filtering off unreacted monomer. After completing the reaction catalyst salts may be filtered off, followed by evaporation of the solvent or by precipitation of polymer in a suitable liquid phase, filtering the precipitated polymer, washing and drying.
The resulting oligomers, polymers, cooligomers and copolymers have a narrow molecular weight distribution. Preferably the polydispersity Mw/Mn is between 1.0 and 2, more preferably between 1.0 and 1.5 and most preferably between 1.0 and 1.4.
Preferred molecular weights Mn are between 1000 and 50 000, more preferred between 1000 and 10 000 and most preferred between 1000 and 5 000.
The process may be carried out in the presence of an organic solvent or in the presence of water or in mixtures of organic solvents and water. Additional cosolvents or surfactants, such as glycols or ammonium salts of fatty acids, may be present. Other suitable cosolvents are described hereinafter.
If organic solvents are used, suitable solvents or mixtures of solvents are typically pure alkanes (hexane, heptane, octane, isooctane), aromatic hydrocarbons (benzene, toluene, xylene), halogenated hydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether), esters (ethyl acetate, propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutyl ether, ethylene glycol dimethyl ether), or mixtures thereof.
The aqueous polymerization reactions can be supplemented with a water-miscible or hydrophilic cosolvent to help ensure that the reaction mixture remains a homogeneous single phase throughout the monomer conversion. Any water-soluble or water-miscible cosolvent may be used, as long as the aqueous solvent medium is effective in providing a solvent system which prevents precipitation or phase separation of the reactants or polymer products until after all polymerization reactions have been completed. Exemplary cosolvents useful in the present invention may be selected from the group consisting of aliphatic alcohols, glycols, ethers, glycol ethers, pyrrolidines, N-alkyl pyrrolidinones, N-alkyl pyrrolidones, polyethylene glycols, polypropylene glycols, amides, carboxylic acids and salts thereof, esters, organosulfides, sulfoxides, sulfones, alcohol derivatives, hydroxyether derivatives such as butyl carbitol or cellosolve, amino alcohols, ketones, and the like, as well as derivatives thereof and mixtures thereof. Specific examples include methanol, ethanol, propanol, dioxane, ethylene glycol, propylene glycol, diethylene glycol, glycerol, dipropylene glycol, tetrahydrofuran, and other water-soluble or water-miscible materials, and mixtures thereof. When mixtures of water and water-soluble or water-miscible organic liquids are selected as the aqueous reaction media, the water to cosolvent weight ratio is typically in the range of about 100:0 to about 10:90.
If more than one polymerizable compound of formula (I) is used, copolymers with different light stabilizer structures are formed. These copolymers may be either random or block copolymers. Because the present polymerization is a xe2x80x9clivingxe2x80x9d polymerization, it can be started and stopped practically at will. Furthermore, the polymer product retains the functional alkoxyamine group or the -Hal group allowing a continuation of the polymerization in a living matter. Thus, in one embodiment of this invention, once the first polymerizable compound of formula (I) is consumed in the initial polymerizing step a second polymerizable compound of formula (I) can then be added to form a second block on the growing polymer chain in a second polymerization step. Therefore it is possible to carry out additional polymerizations with the same or different compounds of formula (I) or with other suitable monomers to prepare multi-block copolymers. Furthermore, since this is a radical polymerization, blocks can be prepared in essentially any order. One is not necessarily restricted to preparing block copolymers where the sequential polymerizing steps must flow from the least stabilized polymer intermediate to the most stabilized polymer intermediate, such as is the case in ionic polymerization.
The process is particularly useful for the preparation of block copolymers containing different light stabilizer groups in blocks in the copolymer. A typical example is a block copolymer containing a hydroxy-phenyl-benzotriazol or a hydroxy-phenyl-s-triazine UV-absorber in one block whereas the other block is build from a 2,2,6,6,-tertamethyl-piperidine group.
In addition to the polymerizable compounds of formula (I) conventional monomers can be used as comonomers, which may be desirable in some cases.
Suitable amounts of other comonomers c) are from 1% to 50% by weight based on total monomers.
Suitable ethylenically unsaturated monomers or oligomers have been already given.
The initiator/regulator compound b1) is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
The majority of compounds of formula (Ia) to (Ij) are known and can be prepared according to standard methods.
Examples wherein the light stabilizer is a hydroxy-phenyl-triazine are given in EP-A-0 434 608, U.S. Pat. No. 5,189,084 or U.S. Pat. No. 5,672,704. Examples wherein the light stabilizer is a hydroxy-phenyl-benzotriazole are given in U.S. Pat. No. 4,785,063 or U.S. Pat. No. 5,112,912. Examples of suitable functionalized benzophenones are given in J. Polym. Sci. (1982), 27(7), 2605-13.
Polymerizable sterically hindered amines (2,2,6,6-tetramethyl-piperidines) are for example disclosed in U.S. Pat. No. 4,210,612, U.S. Pat. No. 4,294,949 or U.S. Pat. No. 4,276,401.
Polymerizable sterically hindered amines from the classes of morpholinone, piperazinone and piperazindione are disclosed in WO 99/14206, GB 2 333 774 and GB 9913511.3.
Definitions and preferences for the different groups and substituents have been given above, they apply also for the process.
The source of radicals in component b2) may be a bis-azo compound, a peroxide or a hydroperoxide.
Preferably, the source of radicals is 2,2xe2x80x2-azobisisobutyronitrile, 2,2xe2x80x2-azobis(2-methylbutyronitrile), 2,2xe2x80x2-azobis(2,4-dimethylvaleronitrile), 2,2xe2x80x2-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1xe2x80x2-azobis(1-cyclohexanecarbonitrile), 2,2xe2x80x2-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl-2,2xe2x80x2-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2xe2x80x2-azobis(2,4,4-trimethylpentane), 2,2xe2x80x2-azobis(2-methylpropane), 2,2xe2x80x2-azobis(N,Nxe2x80x2-dimethyleneisobutyramidine), free base or hydrochloride, 2,2xe2x80x2-azobis(2-amidinopropane), free base or hydrochloride, 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2xe2x80x2-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide.
Preferred peroxides and hydroperoxides are acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate, t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate, t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetyl peroxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate, bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butyl permaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate, t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butyl peracetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 bis (t-butylperoxy) propane, dicumyl peroxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy 3-phenylphthalide, di-t-amyl peroxide, xcex1,xcex1xe2x80x2-bis(t-butylperoxy isopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butyl peroxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide, 3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-xcex1-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.
These compounds are commercially available.
If more than one radical source is used, a mixture of substitution patterns is obtainable.
If b2) a free radical source and a stable free radical are applied separately, the stable free radical is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
The molar ratio of the radical source to the stable nitroxyl radical may be from 1:10 to 10:1, preferably from 1:5 to 5:1 and more preferably from 1:2 to 2:1.
If b3) is applied, the compound of formula (III) 
is preferably present in an amount of from 0.1 mol-% to 30 mol-%, more preferably in an amount of from 0.1 mol-% to 20 mol-%, and most preferably in an amount of from 0.5 mol-% to 10 mol-% based on the monomer or monomer mixture.
A catalytically effective amount of an oxidizable transition metal complex catalyst is preferably 100 ppm to 1%, more preferably 100 ppm to 5000 ppm based on the monomer or monomer mixture. Preferably the molar ratio of complexing agent to transition metal is from 1:5 to 5:1, more preferably from 2:1 to 1:2.
If the process b3) is applied the resulting polymer oligomer contains at its end a halogen atom. This halogen atom can be exchanged by reacting a stable free radical Yxc2x7 with the oligomer or polymer. In this case the free radical is attached to the polymer and the halogen atom is removed. The exchange process is described in PCT/EP 99/06924.
Another subject of the invention is a oligomer, polymer, cooligomer copolymer obtainable by the above mentioned processes.
Still another subject of the invention are the compounds 1,1,3,3-Tetraethyl-2-(1-phenyl-ethoxy)-2,3-dihydro-1.H.-isoindole, 1-(1,1,3,3-Tetraethyl-1,3-dihydro-isoindol-2-yloxy)-cyclohexanecarbonitrile or N-(1,1,3,3-tetramethyl-butyl)-N,O-bis-(1-cyano-1-methyl-ethyl)-hydroxylamin. These compounds used as polymerization regulators PR3, PR4 and PR5 are new.
The oligomers, polymers cooligomers or copolymers obtained by the present process are useful as light or heat stabilizers, particular UV-light stabilizers of organic materials. Preferred organic materials are natural or synthetic polymers. Examples are given below.
The term heat or light stabilizer in the context of the present invention means stabilization against the influences of heat and/or actinic or electromagnetic radiation ranging from xcex3 to infrared.
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density arid high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins; i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerization (normally under high pressure and at elevated temperature).
b) b catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either xcfx80- or "sgr"-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or, IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density. polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(xcex1-methylstyrene).
6. Copolymers of styrene or xcex1-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or xcex1-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from xcex1,xcex2-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl-halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplazstic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
Still a further subject of the present invention is the use of a oligomer, polymer, cooligomer, or copolymer of formula (III), (IIIa); (IIIb), (IIIc), (IIId), (IIIe) or (IIIf) as light stabilizers for organic materials, particularly for natural and synthetic polymers.
Most preferred are thermoplastic polymers and crosslinked polymers, such as thermosetting enamels, paints, laquers and varnishes.
Also subject of the present invention are organic materials stabilized against UV-light with a oligomer, polymer, cooligomer or copolymer of formula (III), (IIIa), (IIIb), (IIIc), (IIId), (IIIe) or (IIIf).